Monoazo dyestuffs and a process of making same



Patented Sept. 27, 1949 "MONOAZO DYESTUFFS5AND.A YRKIGE'SS IOF MAKINGTSAME Willy Steinemann, "Basel, i'szwitzerland, oassignor to San'dozILimitc'd, Fri-hourg, 5 Switzerland, a

.NoiDrawing. Application -August 7, -1945,'*'Serial "No.609499. ""In'SWitzerlari'd' Septeniberfl,1944

4 Claims. 1

The presentnnvention relates to new monoazo dyestufis and their chromecomplex compounds which dye animal fibres in green, blue and grey shadesand to a .process for their preparation.

It has been found that new valuable monoazo dyestuffs can-:b'e preparedby coupling .ldiazotized oamizno-phenoist'ilphonic acids or theirderivafives-"substituted "in the -:nucleus, --with --1--(l-hydroxynaphthyl) .-canbamic acid alkyl uesters rand transforming-theazodyestuffs'thus obtained into thelr-ohromecomplex compounds ontheiibreor in substance. 7

As diazo compounds which are useful fordthe preparation of the newidyestufis'the""foll'owing compounds may be enumerated: 2-aminophen ol-4-sulphonic acid, .z-aminoph-enol i. 6 disu1p'honic acid,:4:chloro-2-aminophenol-fi-sulphonic acid,6-ch1oro;2-aminopheno1-4-su1phonic "acid, "314.6- trich1oro2-aminophenol 5 sulphonic acid, 4-

nitro-Z-aminophenol fi sulphonic acid, '6=nitro-2-aminophenol-4-su1phonic acid, 4-chloro 2- aminophenol 5 sulphoni acid,4-methyl-2- aminophenol eesul phonic acid, -*4benzey1aminoaimmophenolimaiibamic aoiii thylester e s'iil phonic acid,z-amin-ophenol 'fi cai bamic "acid ethylester-l-sulphonic acid and. soon.

'l he coupli-ng compounds which are used ac- 1- (7 -hydroxynaphthyl)-car'b amic ester M. P. 104 C.

1- (7-hydroxynapht'hyl) -carbamic ester M. P. 118119 C.

1 ('7 -=hydroxynapltthyl) -carbamic ethylester) M. P. 116 C.

1- (7 -hydroxyn aphthyl) carbamic acid-n -butylester M. P. 154-155 C.(with decomposition) acid ethylacid- (B-chlor- The coupling of the newcompounds with the diazo derivatives listed above is carried out in theusual way, the azo dyestuffs being obtained with a good yield.

acid methyl- .12 I 'fi hernem'iwell icrystallizi-ng dyestuffs eareiexcel- -lfentaafterechroming idyestufis, most-rofuthem' beningwary-suitable for: .thersoe-called monochromedyeing process. They canalsorbe transi'ormed in substance into valuable, also Well crystallizedchrome complex compounds, in connection with which it has been observedthat the carbamic acid ester group is not saponified in mineral me---di-um. The-chrome-freedyestuffs dye-wool ac- 1-0 xrcording :t-o thewaiter-chronicor :r monoc'hnomedyeing-process in greyygreenish-blue,and-olive V shades :1 of .good .fastnessto light and very .good ffastness to washingandmilling. .The chromecomplexcompounds dye wool froman acid bath 15 "in similar, but morefibri lliant shades possessingvaluable. fastness propenties and verygoodieveling quality. i

The iolow-ing-"examples, without being;.limita- 'tive, illustrate thepresentiinvention,tithegpants being by weight.

Example 1 "295 parts of"314:6 trichloro=2=aminophenol=5- sulphonic acidare diazotized-imthe iusualcway and coupledimtha-presenceof-a.calculated 'quantity of sodium carbonate with 23.1 parts of 1-(7-hydroxynaphthyl) -ca.rbamic acid ethyl ester dissolved in 300 parts ofwater in the.:presence of 4 parts of sodium.hydroxide. The dyestufi thusobtained is'saIted-Outand isolated. In dry state it is a darkxbluepowderwhich is soluble in concentrated sulphuric-acid with a bluish-redcoloration. By the monochromeand after-chrome *dyeing'processes itdyes'wool in greenish-blue to -'grey "shades, "which possess excellentfastness 35 propertiesto light, "tomilling and to washing.

, In order to prepare the chrome complex compound thehyestuff isolatedas above described is dissolved in 1600parts 'of'wateraird;after-a'ddition of 75 part-5 0i chrome alum and 25 pants of formicacid,--itis boiled during 24 hours under reflux. The chromecomplex thusformed is salted out and filtered. In dry state it is a dark-blue powderwhich is soluble inconcentrated sulphuric r acid with abluis'h-redcoloration. It dyes wool from an acid-ibath'in level greenish-blueshades cwi-iieh possessegood frfiastnes ytoi lightaa'nd ia 1 verysgoodciastness tOmiH-ing. and-washing.

' Ewample fi 50 22.4 parts of 4-ch1oro-2-aminopheno1-6-su1- fonic acidare diazotized and coupled in presence of a calculated quantity ofsodium carbonate with 21.7 parts of 1-(7-hydroxynaphthy1)-carbamic acidmethylester dissolved in 300 parts of to water in presence of 4 parts ofsodium hydroxide.

The new dyestufi is isolated by salting it out and filtering. In drystate it is a dark violet powder which is soluble in concentratedsulphuric acid with a bluish-red coloration. This dyestufi is anexcellent monochrome dyestufi which dyes wool from a neutral bath inbrilliant blue-green shades possessing very good fastness to washing, tomilling and to light.

For the preparation of the chrome-complex compound, the dyestufi isisolated in the above described manner, suspended in 1600 parts of Watercontaining '75 parts of 10% sulphuric acid and '75 parts of chrome alumand boiled under reflux for 20 hours. After cooling down to roomtemperature, the chrome-complex compound precipitates totally in wellcrystallized form. In dry state it is a dark-violet powder which issoluble in concentrated sulphuric acid with a bluishfastness propertiesto washing and to milling and a good fastness to light.

3. A monoazo dyestufi of the formula HOaS OH OH red coloration. It dyeswool from an acld bath i in blue shades possessing excellent fastness to20 HO3S NZN washing and milling and a good fastness to light.

The following table shows a number of examples of dyestuffs preparedaccording to the I present invention: N02 0 O a1ky1 Shade of the Diazocompound Azo compound i gs zg chrome complex 14-chloro-2-amino-pl1cnol-6-sulphonlc acidl-(7-hydroxynaphthyl)-carbamicacid-ethylester. bl 2 do l-(7- hydrxl71laphthyl)-carbam1c acid-nbutyl- 13 es er. 3 do 1-(7- ydrynaphthyl)-carbamic .acid-(fl-chlor- Vi 1et-g1-ey ethyD-ester. 44-ch1oro-2-amino-phenol-Ea-sulphonic acid1-(7-tl1ydroxynaphthyl)'carba1nic acid-ethylbl GS GI. 52-aminopl1enol4.G-disulphonic acid..." 1-(7-hydroxynaphthyl)-carbamicacid ehylester. blue-grey. 6 6-nitro-2-amino-phenolA-sulphonic ac d dgrey b1ue 7 44.1itro-2-ainino-phenol-6-sulphon1c acid 01ive gmen 84-methyl-2-amino-phenol-5-sulphon1ca b1ue grey 92amminophenol-4-sulphon1c acid i h 1 blue 104-benzoylamine-2-amn1ophenol-6-sulphon cac d b111e grey bluefiffly 116-benzoylamino-2-am1nophcnol-4-sulphon1c ac1d reddish 1 bhw 122aifiinopheniol-4-carbamic ac1dethyl-ester-6-su1- b1ue grey greenish bhmp onlc aci 13 2. ,min phen01-6-carbamic acid-ethylester-4-suld .do blue.

phonic acid.

What I claim is:

which dyestuff, on treatment with chromium, produces on wool olive-greenshades possessing very good fastness properties to washing, to millingand to light.

2. The chrome-complex compound of the monoazo dyestuff of the formulawhich compound is soluble in sulphuric acid with a bordeaux-redcoloration and dyes animal fibres in olive-green shades possessingexcellent which compound is soluble in sulphuric acid with abordeaux-red coloration and dyes animal fibres in olive-green shadespossessing excellent fastness properties to washing and to milling and agood fastness to light.

WILLY STEINEMANN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,731,643 Wagner Oct. 15, 19292,276,174 Fleischhauer Mar. 10, 1942 2,288,518 Fleischhauer June 30,1942 2,447,163 Conzetti Aug. 17, 1948

